Monoazo dyestuffs insoluble in water



UNETED STATES PATENT OFFICE MO'NOAZO D'YESTUFFS INSOLUBLE IN WATER ErnstFischer, Ofienbach-on-the-Main, Germany, assignor to General AnilineWorks, Inc., New York, N. Y., a corporation of Delaware No Drawing.Application September 1, 1937, Se-

rial No. 162,057. 1936 5 Claims.

The present invention relates to monoazo-dyestuffs insoluble in water;more particularly, it relates to dyestuffs of the following generalformula:

2 OO.NH/

wherein the benzene radical a may be further 7 substituted, forinstance, by alkyl-, alkoxy-,

aryloxy-groups or halogen, R1 and R2 stand for hydrogen, alkyl, aryl,aralkyl or hydroaromatic radicals and the diazo-radical D stands forcompounds of the following formula:

X/ I wherein X1 stands for hydrogen, alkyl, alkoxy or halogen, X2 and X3stand for hydrogen, alkyl, alkoxy, halogen or the group -NH.CO.R3, R3being alkyl, aryl, aralkyl or a hydroaromatic radical, always one of thethree substituents X1,

X2 and X3 being an alkoxy group and always one of the two substituentsX2 and X3 being the group NH.CO.R2', Z stands for hydrogen, halo gen oralkoxy, Z being alkoxy in case X2 stands for the group -NI-I.CO.R3 andsimultaneously X1 or X2 represents hydrogen or halogen.

I have found that valuable violet to blue monoazo-dyestufis may beobtained by combining the diazo-compound from an amine of the generalformula:

wherein X1 stands for hydrogen, alkyl, alkoxy In Germany September 4,

or halogen, X2 and X3 stand for hydrogen, alkyl, alkoxy, halogen or thegroup NH.CO.R.3, R3 being alkyl, aryl, aralkyl or a hydroaromaticradical, always one of the three substituents X1, X2 and X3 being analkoxy group and always one of the two substituents X2 and X3 being thegroup -NI-I.CO.R2, with an arylide of Z-hydroxynaphthalene-3-carboxylicacid of the following general formula:

R1 10 so N 2 wherein the benzene radical a may be further substituted,for instance, by an alkyl, alkoxy, aryloxy group or halogen, R1 and R2stand for hydrogen, alkyl, aryl, aralkyl or hydroaromatic radicals and Zstands for hydrogen, halogen or alkoxy, Z being alkoxy in case X2 standsfor the group NH.CO.R3 and simultaneously X1 or X2 represents hydrogenor halogen, only such dyestuff components being used as do not containany group lending solubility, such as the 1 sulfonic or carboxylic acidgroup.

The dyestufis can be produced in known manner on the fiber (native orregenerated cellulose) in'substance or on a substratum. They mayadvantageously be used for the manufacture of 3 -very fast color lakesand for coloring cellulose esters and ethers, natural and artificialresins, organic plastic masses of high molecular weight as, forinstance, products made from nitro-cellulose, resins prepared fromformaldehyde and 5 urea, phenols or amines, vinyl resins, natural rubberand the synthetic products which have a constitution and propertiessimilar to those of natural rubber. The rubber dyeings thus obtained areof great techincal Value, since the new 4 dyestuffs are insoluble inbenzine, fast to vulcanization, very fast to light and do not bleed intowhite rubber during the vulcanization process. Especially with regard tonon-bleeding the dyestuffs of the present invention are distinctlysuperior to the comparable combinations which are described in Germanpatent specification 486,190 as well as to the blue water-insolublemonoazo-dyestufi, described in German patent specification 508,585, fromdiazotized 4-amino4'- methoxydiphenylamine and1-(2'-hydroxynaphthalene-3 -carbonylamino) -2-methoxybenzene-5- sulfonicacid dimethylamide.

The azo-components used in the present process may be prepared accordingto the process of British patent specification 281,795.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto.

(1) The material is grounded with 6 grams per liter of2,3-hydroxynaphthoyl-1-amino-2'-chlorobenzene-4'-sulfodiethylamide anddeveloped in known manner in a neutralized diazo-solution from 3 gramsper liter of l-amino-2,5-diethoxy- 4-benzoylaminobenzene, then rinsedand soaped. A violet dyeing of good properties of fastness is obtained.The dyestuff corresponds with the following formula:

NH.CO.CQH5

O CaHu S OzN When in the same manner 2,3-hydroxynaphthoyl-laminobenzene-l-sulfo-N-methyl ben zylamide is used as couplingcomponent,a reddish blue dyeing of similar properties is obtained.

(2) 15 grams of 1-amino-2,5-diethoxy-4-benzoylaminobenzene are-diazotized in the usual manner. Thereupon the diazo-solution is mixedwith sodium acetate in order to bind the excess of'hydrochloric acid andthen stirred into a solution of 21.2 grams of -2,3-hydroxynaphthoyl-1-(3) A pigment dyestuff which is adapted for coloring rubber products isprepared as described in Example 2. 4 per cent. of this dyestufi areincorporated with a suitable mixture of rubber. loading materials,sulfur and a vulcanization accelerator and the mixture is vulcanized ina vulcanizing press, while hot. There is obtained a blue vulcanizatewhich has a good fastness to light and neither bleeds into white rubber,nor gives rise to the phenomenon which is known as bluishing orefflorescence when the rubber articles are stored.

(4) 13.6 grams of l amino-2,5-dimethoxy-4- benzoylaminobenzene arediozatized in the usual 'manner. The diazo-solution which has beenrendered neutral to Congo red paper by means of sodium acetate isstirred into a solution of 21.6 grams of2,3-hydroxynaphthoyl-1'-aminobenzenel' sulfobenzylamide in dilutecaustic soda solution. The-blue dyestuff obtained is filtered withsuction, well washed and dried.

It yields .bluetrubber dyeings which are fast to vulcanization and havevery good properties of fastness, when a mixture of rubber, the usualadmixtures and 4 per cent. of the dyestuff is immersed ina solution ofsulfur chloridev in benzine and vulcanized in the cold.

(5) 22.6v grams of 2,3-hydroxynaphthoylelamino-3'-chlorobenzene-4-sulfanilide are dissolved in water and thenecessary amount of caustic soda solution and reprecipitated with aceticacid, while well stirring. Into this suspension there is introduced,while stirring, a diazosolution prepared in the usual manner from 12.8

grams of 1-amino-Z-methoxy-S-methyl-4-ben-1,35

zoylaminobenzene while simultaneously adding the quantity of sodiumacetate necessary for binding the excess of mineral acid. Whencoupling-iscomplete, the violet dyestufi formed-is filtered withsuction, well washed and dried. 'It 240 may. .be'. used for coloringcasein artificial-horn in the f ollowing' manner:

-'A:mixture.is'prepared from 200 gramsof rennet casein, 8 grams of zincwhite and lgram'Of I, v amiriobenzgne 41 sgiilfocycIl ghexylamliled 1 10 31? the dyestufi and hardened by treatment with .45 9 9 8 Separa 8 yformaldehyde. A violet horn-like mass is ch- 15 illtered with suction,well washed and dried. tained which has very good properties of fast- Itforms a blue powder. The lakes gprepared mess, there rom n k w mannerP085658 I D" The following table illustrates a series of otherertiesofefastness. dyestuffs which may be prepared according to Thecombinationmay also be effected in the the present invention and areespecially adapted presence of 1a substratum adapted-for theprepfor'coloring high .molecular organic plastic aration of. color..lakes.masses:

Dyestufifrom- Shade 1 Diem-compound oi Coupled with--2,3-hydroxynaphthoyl-l-an1ino- 1l-ammo-2,5-diethoxyiabenzoylammobenzene. -benzene-4-sulio-n-butyla;mideBlue. 42 o .-2-methylbenzene-4(-sulfo-N-methylanilide.. Rcddishblue. '3l-amino-2,5-dnnethoxy-i-benzoylaminobenzen-2,5-dimethoxybenzenevefrsullodimethylamide Violet.

&, o -2-methylbenzenc-4-sulio-N-methylauilide. 'Reddish' blue. 5l1%mmo-2,5 dicthoxy-4-.(2.5rd1ehloro-).bcnzoylamino-:2-chlorobenzene-4-sulio-diethylamide Do.

' enzene. 6 Lamina-2,5-dimcthoxyi-(alpha-)naphthoyl-aminoben--=benzene-4-sulfo-N=methyl-benzylamide. Blue.

.zene. 7 l-arnino-2-methoxy-5-methyl-4-benzoylamino benzene.-benzcue-4-sulio-cyclo-hexylamide. Violet. 60 8 l-amndZA-dunethoxy-5-benzoylairunobenzenaabenzene-4-sulfo-N-methyl-benzylamide Do. 9, I-amno-Z'methoxy-5-chloroi-bcnzoylaminoebenze-Z-methylbenzene-4-sulfo-N-1nethylanilidc .Do. l0 l-ammo 2,fi-diethoxyiphenacetylaminmbenzenc.. '-benzene--i-sulfo-cyclo-hexylamide Rcddishblue. -1l .1-ammo 2,5=diethoxy 4-hoxahydro-bcnzoylrsrninoben-I-benzenc-4-sulianilide .i Violet.

. zone. 12 lamina-2,5-dimethoily-4-benzoyiaminobenzene- -benzcne-isulio-cyclo-hexylamide Blue. 113 l-amino-2,fidimethoxy4-acetaminobenzene i .-benzene-4-sullanilide Violet. .7'0 .44do -2-chlorobenzcne-4-sulfo-diethylan do Do. 15I-ammo-Z,5-d1etl1oxy-4-benzoylammobenzene. '-benzene-4-su lfanllideBlue. 16 1 do -benzene-4-sulfodiethylamide Violet. 17;-benzene-4-sulfo-N-ethylcyclohexylamide.- Do. 18'--2-chlorobeuzene-4-sulfoethylamido Blue. 19---2-methylbenzene-4-(sulfo-2-amino-1,2,3,4-tetra- Do.

hydronaphthalene) Dyestufi from- Shade Blaze-compound of Coupled with-2,3-hydroxynaphth0yl-1-amino- 20 1-amino-2-methoxy-5-benzoylaminobenzene-2-ch10r0benzene-4-sulfodiethylamide Violet 21l-amino-2-methoxy-S-methyl-4-benzoylaminobenzene. -benzene-4-sulfanilideDo. 22 1-an1ino-2,5-diethoXy-4-benzoylaminobenzene -benzene-4-sulfamideBlue. 23 do -be11zene- 4-sulfo-diphenylamide Do. 24-be11zenc-4'-sulfo-N-benzylanilide Do. 25 -benzene-4-sulfo-dibenzylamideDo. 26 -benzene4-sulf0-N-benzylcyclohexylamide Do. 27-3-cl1l0r0benzene4-sulfanilide Violet. 28-benzene-4-(si1lfo-2-ami11o-naphtl1alene). Blue. 29-benzene-4-sulfo-dicyclohexylamide l- Reddish blue. 30 ,olmethoxy-4-benzoylaminobenzena-2,5'-diethoxybenzene-4-sulfodimethylemide. inlet. 31l-amino-z-methoxyi-aeetaminobenzene .l -benzene-4'-sulfanilide Do. 32l-amino-3-methoxy-4-benzoylaminobenzene -benzene-4-sulfodiethylamide Do.33 l-amino2-methyl-5-Inethoxy-l-benzoylaminobenzene.-benzene-4-sull'odiethylaniide Do. 34l-amino-2-cl1loro-5-methoxy--beuzoylaminoben zene.-benzene-4-sulfanilide Do. 35 l-amino-2,4-diethoxy-5-benzoylaminobenzene-benzenc-4-sul1'a11ilide Do.

6-bromo-2,3-l1ydrox ynaphthoyl-l no- 36l-amino-2,5-diethoxy-ibenzoylaminobenzene -benzene-4"sulfanilide Blue.

6-methoxy-2,3-hydroxynaphthoyl-l-amino- 37l-amino-Z-methoxy-fi-benzoylaminobenzene -benzene-4-sul[anilide Reddishblue. 38 l-amino-Q,5-diethoxy-kbenzoylaminobenzene--benzene-4-sulfanilide Blue. 39 l-amino-4-methoxy-5-benzoylaminobenzene-benzene-4-sulfanilide Violet.

Since an object of the present invention is to provide dyestuffs of goodfastness properties which dyestuffs are insoluble in water and alkalies,it is to be understood that the aromatic nuclei of the general formulaeappearing in the appended claims do not contain any substituents whichare known to render organic compounds soluble in water or alkalies andto tend to depreciate the fastness of the dyestuffs to alkalies.Substituents of this kind are, for instance, the sulfonic acid and thecarboxylic acid group.

I claim:

1. The water-insoluble monoazo-dyestufl's of the following generalformula:

D 111 1 T Y2 R1 0 H I S O 2.N

z o 0 .NH

wherein R1 and R2 stand for members of the group consisting of hydrogen,alkyl, aryl, benzyl and hydroaromatic radicals, Y1 and Y2 stand formembers of the group consisting of hydrogen, alkyl, alkoxy and halogenand the diazo-radical D stands for compounds of the following formula:

wherein X1 stands for a member of the group consisting of hydrogen,alkyl, alkoxy and halogen, X2 and X3 stand for members of the groupconsisting of hydrogen, alkyl, alkoxy, halogen and the group NH.CO.R3,R3 being a member of the group consisting of alkyl, benzyl, a radical ofthe benzene and naphthalene series and a hydroaromatic radical, alwaysone of the three substituents X1, X2 and X3 being an alkoxy group andalways one of the two substituents X2 and X3 being the group NH.CO.R3, Zstands for a member of the group consisting of hydrogen, halogen andalkoxy, Z being alkoxy in case X2 stands for the group -NH.CO.R3 and oneof the Substituents X1 and X3 for a member of the group consisting ofhydrogen and halogen, yielding fast violet to blue lakes and, when mixedwith rubber products, violet to blue colorations of very good fastnessto light and to vulcanization.

2. The water-insoluble monoazo-dyestufis of the following generalformula:

NELC 0.051;,

o 0.NH

monoazo-dyestuff of NIELCO-CuHs CHHE'O OH S O2-NH-OQH5 c O.NH

yielding fast blue lakes rubber fastness yielding fast blue lakes and,when mixed with rubber products, blue-colorations of very good fastnessto light and to vulcanization.

5. The water-insoluble omonoazov-dyestufi of the following formula:

NH-C O .0511;

CHzO

N II

CO.NH

rubber products, violet fastness to light and to vu lcanization.

ERNST FISCHER.

